Polyhydric phenol-bisulfite addition product composition and method for cold waving



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United` States Patent O POLYHYDRIC PHENL-BHSULFITE ADDITVIGN PRODUCT COMPSITN AND METHD FOR COLD WAVING i Anacleto Mora, Milan, Italy, assignor, by direct and mesne assignments, of one-half to Nathalie Wollard, New York, N. Y., and one-half to Anacleto Mora, Milan, Italy No Drawing. Application April 7, 1954, Serial No. 421,709

11 Claims. (Cl. 132-7) sively chemical nature (treatment at room temperature).

Because of their simplicity, the methods of. chemical nature have attained the widest popular use and the largest distribution. They are called cold waves and it is with respect to them that we shall be concerned in this `disclosure.

Such cold wave methods are based either on the capacity of the chemicals used to cause the swelling of the keratinous materials, or on their ability to break the disulphide bonds of the cystine, which is the main constituent of the keratin and on the successive transformation of the cystine into cysteine, the alteration of the hair dining that state of constitution, and the retransformation or regeneration into cystine by the action of oxidising agents, after the hair has taken the desired form. When the cystine is considered an amino-aci'd-thiol, it is easy to consider the reactions as based on the part taken by the hydrogen atom of the thiolic group, on account of it-s lability, in the oxidizing-reducing reactions.

Thus particularly:

2R.SH

HzN NH2 cystine CH-CHl-S-S-CHT-C HOOC COOH The means used for breaking the disulphide bonds by chemical agents are numerous. Mercaptans as thioglycolic acid (patent of Everett G. McDonough No. 2,577,710) have been preferred and largely used. On the other hand, the metallic sulphides (U. S. Patent l5. PyeVNo. 2,183,894) have been used but have new been wholly given up because of the serious inconveniences in their use, the main of which consists of the impossibility of stopping their reducing action at the right time. The sulphites, bisulphites, metabisulphi'tes either with organic or metallic radicals, while largely used for the socalled hot wave, have been employed in the cold wave method with very inferior results. Hence, at the present Cysteine Cystine 2,783,762 VPatented Mar. 5, 1957 ICC o time, no efficient cold wave method based on such products maybe found in the trade, so far a-s we know. The following patents represent the state of theAart.

U. S. A.-No. 2,095,374, patent applic. 1932 (R. Steinbach) DR.-No. 635,845, patent applic. 1934 (Coriolan CmbH.)

B. P.-No 423,845, patent applic. 1933 (Norman) U. S. A.No 2,400,377, patent applic. 1934 (Speakmann) v U. S. Ana-No. 2,351,7l8,'patent applic. 1935 (Speakmann) B. P.-No 444,312, patent applic. 1935 (Norman) B. P.-No. 465,881, patent applic. 1937 (Rodney) B. P.-No. 468,845,` patent applic. 1937 (Erwin) U. S. A.-o. 2,155,178, patent applic. 1.936 (Brown) B. P.o. 532,285, patent applic. 1.941 (Norman) B. iff-No. 550,746', patent applic. 1942 (Backer) U; S. A.No. 2,410,248, patent applic. 1.946 (Speakmafm). B. P.-No. 472,745y patent applic. 1.937 (Norman) U. S. A.-No. 2,437,965, patent applic. 1944 (Michaels) We have ydiscovered that, contrary to the arntations the justness of suolil an. assertion resides in the tact that the curling power' ofthe mercaptans", and in particular of thioglycolic acid, which undotibtly possesses a high breaking capacity for the bisulphid'e bonds, is practically null ander a pH of 8, whereas it is quitesufflcient at a higher pH, viz.: between 9 and l0, Because" only at such a high pH do tite solutions of tnerc'aptan acids present a good hydfoiizing capas-ity for keratino-n's niaterials. It is evident from the' above, that only when the optimum properties of breaking' the' disulphide of the cystine bonds is joined to a goed hydrolfizing and swelling: capacity olf the keratinous material is it possible to obtain an etlicient and permanent curling or waving of thehair in thel cold.

Technically the thioglycolates give very good results, vbut their use is not exempted troni serious inconvenience; The vuse of. thioglycolates in the sti-'called cold wve fre'- qnently leads to a deep and' irreversible morphologie deformation of the hair,l which suers a definitive m'dication of. its physico-'chemical structure. Also cases of poisoning, ndf of alteration' of the cutaneous tissues of theT persons who handle products containing thioglyc'olic acid bases are frequently notedj` the literature gives inany of such cases arl'd there arev manyr publications on the point?.

Furthermore, th'ef odor and;A exhalations of such com*- positions are not always suterable aind cause many people to suffer from loss of appetite', headache, irritation of the eyes, stomachl trouble,- and dizziness.

The neutral and acid salts of they anion H803', containing a metallic or organic cation' combined with the' H803', have been used for decades in li'q'uid compositions? for het waves, and? their use has been' transferred to the coldi Wave technique; they haveV numerous' advantages over mercaptans, viz-.z they have a v'er-y low level of toxicity, which may be considered zero under normal conditions; they have no= dis'ageeableodor and' they have very goedv solubilityv and stability in solution at the' v-r'iouspHis used for waving. However, they have' ai ne'ga- ,tiyef property of great practical` importance, thev lovv abi-1"- i-ty- 'of-i 'slphitesgt ,bisulphtea.metasilphites,V thosulplifes to break a suiilcient quantity of bisulphide bonds of the cystine contained in the keratinous-material at room temperature, in a short time. Clarke (J. Bil. Che. 19321 9?@235) has indeed demonstrated that bisulphites will reduce into cysteine only one half of the cystine submitted to the treatment, whereas the other half is transformed to sulphonic S-cysteine acid:

NHQ SOzH-S-CHz-C COOH which is not reversible into cystine. It follows as a consequence that in the processes based on the use of sulphites, bisulphites, etc. only one half of the bisulphide bonds of the cystine may be regenerated by the oxidizing treatment to which the keratinous material is submitted, the other half being practically lost, because the sulphonic S-cysteine acid is not reversible into cystine.

For the foregoing reasons, the methods till now applied for curling or waving keratinous materials at room temperature with derivatives of the HSOs anionV have been imperfect. Furthermore, those methods require too long a period of contact with the hair to be interesting to the trade; they exert a modifying action on the structure of the keratinous material by virtue of their hydrolyzing power rather than by breaking the bisulphide bonds, and the hydrolyzed material may not be reconverted by the successive oxidizing operation.

On account of bad elfects resulting from long contact of the hair with the waving liquids, as specified in the various prior art patent specifications dealing with the subject, the liquids must be either acid or alkaline to reduce the time of Contact and they are accordingly possessed of a marked hydrolyzingpower, they swell the hair and the swelling is hard to remove, and the wave that results does not possess suficient properties of elasticity, and is weak and without vitality. Furthermore, the long contact of the bisulphites, especially of those with metallic cations of acid or alkaline pH, causes hair decoloration. These deciencies are the more apparent as the treatments are made on hair that had previously been oxygenated or dyed. A particular hydrolyzing and hair swelling has also been discovered to result from the use of the bisulphites derived from organic bases.

It is an object of this invention to produce a nonpoisonous waving solution which combines the optimum properties of breaking the disulphide bonds of the cystine with good hydrolyzing and swelling capacity for the keratinous material, and thus to obtain an eiiicient and .permanent curling and waving of the hair in the cold.

It is another object of the invention to Wave hair at room temperature adequately, quickly, with a contact with the waving liquid on the order of 10-30 minutes, without appreciably swelling or permanently modifying the chemical structure, color,` state, or nature of the hair, with a solution of pH in the neutral range, without irritation to the skin, without harmful effect on the operator or the subject, and without disagreeable odors.

The objects of the invention are accomplished, generally speaking, by the use, in the waving of hair, and particularly in the cold waving of hair, of compounds resulting from the reaction of metal, and of amine, bisulites on polyphenols. The class of polyphenols is preferred which will react in its tautomeric (ketonic) form. The compounds are prepared from the polyphenols and the amine or metal bisultes with a pH in the neutral or alkaline range, from pH 6 to pH 9, and are used in aqueous Ymedium as lotions which require only a reasonable time to produce the necessary change in the keratin and may thereafter be washed'out with oxidizing solutions which regenerate the constituents of the waved hair. The invention includes many advantageous modifications Vbutylamine, propylamine, of alkanol amines such as ethanolamine, of secondary bases such as dimethylamine and diethanolamine and of tertiary amines such as trimethylamine and triethanolamine have been used and illustrate the class of reagents. ln practical use, however, only the primary amines are employed as their resulting products are quite superior to the more complex members of the class. Thus, monoethylamine, monomethylamine, and monobutylamiue are preferred. Monoethanolamine gives acceptable results, but less desirable than those obtained from the preferred compounds. Y

lt has been established that the lotions of the preferred substances possess at room temperature a curling or waving power which is very much superior to that of the prior art bisulphitic solutions. Further, it has been discovered that said derivatives have maximum waving power at a pH about 6.4 to 6.8. Thus, it is possible to produceneutral solutions that are practically odorless, harmless, and eicient.

After having experimented with numerous methods and products, we have discovered that this series of compounds presents the following advantages:

(a) At room temperature to produce durable and technically unobjectionable waving or curling with a contact of the liquids between l0 and 30 minutes;

(b) Absence of appreciable swelling or permanent modification of the chemical structure, and of the state or nature, of the treated materials;

(c) Maximum curling or Waving capacity with a pH the value of which is about 7;

(d) No phenomenon of irritation in the cutaneous tissues;

(e) No disturbing or disagreeable odors.

The derivatives forming the object of this invention, and which have proved in practice to be in possession of a curling or waving capacity superior to that of the derivatives till now used of the bisulphitic anion, are the products of the reaction of polyphenols with the bisulphites of metallic or organic cation. Evidently, the addition of the polyphenolic group, which fulfills in accordance with the cases a more or less marked reducing action, contributes to increase the percentage of cystine reduced to reversible cysteine, and to stop the formation of sulphonic S-cysteine acid which results from the use of simple bisulphites: for this reason the quantity of cystine which can be disposed of is greater, when the denitive reconstruction of the keratinous material is made, and a consequent more integral reconstruction of the primitive state of the same is obtained, when it is submitted to the iinal oxidizing treatment.

As it is known, some polyphenols, and particularly the dihydroxy and trihydroxy-benzenes have the property besides to react normally to also react in their ketonic form; for instance, resorcin may react in its normal structural form (l) or in the ketonic form (2).

o 0H ll on o These ketonic forms of the preferred polyphenols have the property to react with the bisulphites.

So for instance:

The ketonic form of the resorcin combined with a bisulphite gives a product that corresponds with the following formula:

CsHsSaOuRs Paradioxybenzene (hydroquinone) in its ketonic form combined with a bisulphite produces a salt ofthe dihydroxy-1-4-hexarnethylentrisulphonic acid:

Pyrogallol (pyrogallic acid) in the ketonic form combined with a bisulphite produces a bisulphitic derivate of the oxo-3-dihydroxy-S6-tetrahydroxy1-2-3-4-benzensulphonic acid.

Phl'oroglucinol in its ketonic form produces derivates that are diiferent depending upon whether 1, 2 or 3 of the ketonic groups of its tautotneric` form tix the acid salt.

Further, it has been discovered that said derivates give the maximum result at a pI-I between 6' and 9 with an optimum around 7. Thus, it is possible to produce neutral solutions that are practically odorless.

Also the nature of the bisulphitic molecule brought to react with the polyphenols has a certain importance, and, by varying it, it is possible to get a diierentiation of the practical results.

The following examples illustrate, but do limit the invention to the particular reactants and conditions i-n them stated.

Example 1 100 parts by weight of monoethylamine. were dissolved in 100 parts by weight of water and SO2 gas was bubbled through the solution until the pH was in the range 6.4 to 6.8 while maintaining the temperature below about 40 C. In carrying out this portion of, the process, the

pH may sometimes drop below 6.4, inA which case the addition of SO2 should be stopped and enoughmonoethylamine be added to bring the pH within the stated range.

350 parts by weight of the product fromA the foregoing reaction were mixed with 10 parts by weight of hydroquinone in 700 parts by weight of water. 3 parts by weight of stannous chloride (SnClz, ZHzO) were added as a catalyst. The stannous chloride is not essential, as the reaction proceeds without it, but it is beneficial and an additional and valuable part of the invention. solution was allowed to stand for about two days atl room temperature and at that time it had-become golden in color and was ready for use. It was stable, and could be stored for extensive periods of time without loss of eiciency.

In producing the lotion that is used onthe hair, this product was dissolved in an aqueous medium such as pure water. Up to 70% of alcohol can be used if desired in the solution, but in general the lotion is a' simple water solution of the product.

The tin chloride can be replaced by other bivalent salts, for instance, by the halides, particularly the chlorides, of paladium, platinum, rhodium,` bismuth, iron, cobalt and copper, but tin chloride is preferred.

Instead of using SO2 gas for the reaction with monoalkylamine, sodium bisulfrte or sodium hydrosulfite` and their equivalents may be used.

The product of the reaction between monoethylamine and S02 is monoethylaminebisuliite which reacts toform a product having the desired property.

The oxidizers are oxidizing agents soluble in water, such as perborates, persulfates, hydrogen peroxide, perchlorates, chlorates, bromates, and such things as urea derivatives of hydrogen peroxide. The oxidizing agents can be used directly after solution in water, or in the presence of acid, of which tartaric, citric, lactic, phosphoric, hydrochloric and sulfuric may be used.

The'

' 6 Example 2 Monoethylamine was reacted with sulphur dioxide as inv Example I after which 450 parts by weight thereof were taken and mixed with 30 grams of hydroquinone and 3v grams of tin chloride in 820 parts of water. This produced a` solution useful for a different type of hair than that of Examplev l. The water content in the nal product of Example 2 can be varied between 700 and 900 parts and still retain the full utility of the solution, while adapting i-t to diierent types of hair and to different rates of treatment. It is used in the more concentrated range whenv fastaction is desired. Outsidel the stated range of concentration, the eiciency of the solution decreases, although its utility persists.

Excmrple 3 Resorein was reacted with sodium bisulfite producing a compound having the formula NazCeHgSsOn. The technique of Example 1 was employed using sodium bi sulte in place of monoethylamine-bisulfite. The resorcin and sodium bisulte were present in approximately equi molecular parts. The reactants were boiled 8 hrs. under reux with the admission of a light. current of SO2 to the reaction mass. Tm chloride catalyst was used.

l5()` cc. of 99% (glacial)- aceticr acid was dissolved in 350 ce. of water containing H2O2 and was employed in oxidizingl hair4 which had been` treated with the product of Example 3. After the oxidation, the hair was rinsed in lukewarm, pure water; In bothl this example, and in Example- 6, where this' oxidizer was also used',- the hair wasy soft, lustrous', well`l curled and possessed of a very natural appearance. In usingphosphoric acid, amounts equivalent to acetic acid in the present example were successfully employed on hair treated by' the product of Example l.

Example 4 Monomet-hylamine bisulte was preparedr as in the rst part of Example lf and the prod'uct was reacted with hydroquinone utilizing a similar technique.

Example 5 Sodium bisultte was reactedl with: phloroglucinol and similarly employed'.

Inmaking up the working solutions for application to the hair, it isadvisable tocompute the weight percentage of the actual poduct of the polyphenol and bisultite inthe lotion. This. may vary widely, but concentrations for useful solutions lie generally between 3 and 60% by weight.

In applying the solution to the hair, the ends of the hair are to be trimmed, ifthey are split or contain the remains of anI old permanent,` the hair should be shampooed and thoroughly rinsed and dried. Then a wave lotion i's applied to a strand' of hair, the wet strand is wou-nd on abigoudi, and all the hair is similarly done, strand by strand, being wetted with the solutiorrand wound onS curl'ersa When allthel curls are wound, the hair is aga-ini thoroughly Wet with the solution and then enclosed within` a scarf or` a turban for about 20' minutes. The average processing time for easy-to-wave hair, or for hair withsom'e'natural curl, is about 2-0 minutes; for normal hair 3G minutes; andi for children and difficult hair 40 minutes. When the time is up, with the hair still' wound onA curl'ers; it is rinsed'A thoroughly in lukewarm water to remove the lotion, and blotted with a: towel'. The regenerator oroxidi'zer i's now applied and is allowed to remain on the hair for about xe minutes, and the oxidizer is washed out in lukewarm water.

Water, and hair which had been impregnated with the product of Example l was treated thereby.

'7 Example? With a water solution containing 20% circa of the product obtained from the reaction of g. of resorcinol with g. of sodium bisulphite brought to a pH of 7,-71/2 by means of ammonia, the hair is made wet and wound onto higoudis, the head being then covered with a towel and a cap, preferably of plastic material. The solution is left to act for about 15-20 minutes; then the hair is rinsed with abundance of water (lukewarm), and afterwards the bigoudis are wet for live minutes with an acid solution in the quantity of 500 cc. and containing about 10% by volume of hydrogen peroxide. Successively, the bigoudis are opened and the hair thoroughly washed with water. Finally, the usual waving operation may be made.

Example 8 With a water solution containing 22% of thc product obtained from the reaction of 6.3 g. of phloroglucinol with 15.6 g. of bisulphite of sodium brought to a pH of 7-71/2 by means of ammonia, the same operations of Example 7 are made.

Example 9 With u water solution containing 22% of the product obtained from the reaction of 17 g. of bisulphite of monomethylamine with 5 g. of paradioxybenzene brought to a pH of 7-71/2, the same operations as per Example 7 are made.

The solutions are used at room temperature, and it is of importance that the process of transformation of the cysteine into cystine by means of oxidizing agents be made accurately. lt has been observed that theprolonged washing with water only, as specified in several patent specilications, is not sufficient to retransform the cysteine into the cystine contained in keratinous materials, and therefore the curlings or wavings deriving from them are of short duration; for this reason, it is necessary to make use of an oxidizing agent, the efficiency of which will be particularly good if made lightly acid.

The principles of the invention may be employed for straightening curly hair as well as for curling straight hair. Various methods of applying the process to the hair or other keratinous material can be adopted without departing from the scope of the invention.

As many apparently widely different embodiments of the present invention may be made without departing from the spirit and scope thereof, it is to be understood that the invention is not limited to the specific embodiments.

What is claimed is:

l. A method for cold waving of hair, which comprises wetting the hair at room temperature with an aqueous lotion containing essentially 0.5 to 60% of an addition product of one mol of a polyhydric phenol and at least three mols of a bisultite, at a pH of 6 to 9, and thereafter wetting the hair with an oxidizing agent in aqueous medium.

2. A method for cold waving of hair, which comprises wetting the hair at room temperature with an aqueous lotion .containing essentially 0.5 to 60% an addition product of one mol of hydroquinone and at least 3 mols of monoethanolamine bisulte, at a pH of 6 to 9, and thereafter wetting the hair with an oxidizing agent in aqueous medium.

3. A method for cold waving of hair, which comprises wetting the hair at room temperature with an aqueous lotion containing essentially 0.5 to 60% an addition prod- 8 uct of one mol of a polyhydric phenol and at least 3 mols of a bisulte plus a small amount of a bivalent metal halide sufficient to catalyze the formation of said addition product.

4. A method for cold waving of hair, which comprises admixing in aqueous solution one mol of a polyhydric phenol and at least 3 mols of a bisulfite with a catalytic amount of a bivalent metal halide to eifect formation of a polyhydric phenol-bisultite addition product, wetting the hair at room temperature with an aqueous lotion containing essentially 0.5 to 60% of said product, at a pH of 6 to 9, and thereafter wetting the hair with an oxidizing agent in aqueous medium.

5. A method of forming a cold wave lotion, that comprises admixing in aqueous solution one mol of a polyhydric phenol and at least 3 mols of a bisulte, in the presence of a catalytic amount of a bivalent metal halide, and maintaining such solution at room temperature to form a polyhydric phenol-bisulte addition product.

6. A method of forming a cold wave lotion, that comprises admixing in aqueous solution l mol of hydroquinone and at least 3 mols of monoethylamine bisullite, in the presence of a catalytic amount of a bivalent metal halide, and maintaining such solution at room temperature for at least two days.

7. A hair waving lotion consisting essentially of an aqueous solution of 0.5 to 60% of an addition product one mol of a polyhydric phenol and at least 3 mols of a bisulte, at a pH of 6 to 9 plus a small amount of a bivalent metal halide suicient to catalyze'the formation of said addition product. v

8. A hair waving lotion consisting essentially of an aqueous solution of 0.5 to 60% of an addition product of 1 mol of hydroquinone and at least 3 mols of monoethylamine bisullite reacted at room temperature in the presence of a stannous chloride catalyst for at least two days.

9. A hair Waving lotion consisting essentially of an addition product one mol of a polyhydric phenol and at least 3 mols of a bisulte, in a concentration of 0.5 to 60% in a solvent of the class consisting of alcohol and water, at a pH of 6 to 9, also containing a catalytic amount of a metal halide.

10. A composition consisting essentially of 1 mol of a polyhydric phenol and at least 3 mols of a bisullite, in the presence of -a catalytic amount of a metal halide, at a pH of 6-9 in aqueous solution.

ll. A composition consisting essentially of l mol of hydroquinone and at least 3 mols of monoethylamine bisulte, in the presence of a catalytic amount of stannous chloride, at a pH of 6-9 in aqueous solution.

References Cited in the tile of this patent UNITED STATES PATENTS OTHER REFERENCES Lauer et al.: J. Am. Chem. Soc., vol. 56, pp. 1628-9 Fuchs, Ber Deut Chem., vol. 54, pp. 24S-249 (1921). Richter, Textbook of Organic Chem., 3rd ed. (1952), pp. 449-50. 

